5-phenylpyrimidines, their preparation, compositions comprising them and their use

ABSTRACT

5-Phenylpyrimidines of the formula I  
                 
in which the substituents and the index are as defined below: 
     R 1 ,R 2  are hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl, and R 1  and R 2  together with the nitrogen atom to which they are attached may also form a saturated or unsaturated ring which may be interrupted by an ether, thio, sulfoxyl or sulfonyl group and may be substituted by one to four groups R a  and/or R b ;    R 3  is hydrogen, halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy or alkenyloxy;    R 4  is hydrogen, halogen, cyano, hydroxyl, mercapto, azido, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, alkylthio, alkenylthio, alkynylthio, haloalkylthio, —ON═CRN a R b , —CR c ═NOR a , —NR c N═CR a R b , —NR a R b , —NR c NR a R b , —NOR a , —NR c C (═NR c′ )NR a R b , —NR c C(═O)NR a R b , —NR a C(═O)R c , —NR a C(═NOR c )R c′ , —OC (═O)R c , —C(═NOR c )NR a R b , —CR c (═NNR a R b ), —C (═O)NR a R b  or —C(═O) R c ; 
       in which R a , R b  and R c  are as defined in the description; X is halogen, alkyl, alkoxy or haloalkyl; and m is an integer from 1 to 5; processes for preparing these compounds, compositions comprising them and their use for controlling harmful fungi are described.

The present invention relates to 5-phenylpyrimidine of the formula I

where the substituents and the index are as defined below:

-   R¹,R² independently of one another are hydrogen, C₁-C₆-alkyl,    C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,    C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl or    C₂-C₆-haloalkynyl,    -   R¹ and R² together with the nitrogen atom to which they are        attached may also form a saturated or unsaturated five- or        six-membered ring which may be interrupted by an ether- (—O—),        thio- (—S—), sulfoxyl- (—S[═O]—)or sulfonyl- (—SO₂—)group and/or        may be substituted by one to four groups R^(a) and/or R^(b);-   R^(a),R^(b) independently of one another are hydrogen, C₁-C₆-alkyl,    C₂-C₈-alkenyl, C₂-C₈-alkynyl, Cl-C₆-haloalkyl, C₁-C₆-alkoxy,    C₁-C₆-haloalkoxy,    -   C₃-C₁₀-cycloalkyl, phenyl or a five- to ten-membered saturated,        partially unsaturated or aromatic heterocycle containing one to        four heteroatoms from the group consisting of O, N and S, where        the cyclic radicals may be partially or fully substituted by the        following groups R^(x):        -   R^(x) independently of one another are cyano, nitro, amino,            aminocarbonyl, aminothiocarbonyl, halogen, hydroxyl,            C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkyl-carbonyl,            C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl,            C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkyloxycarbonyl,            C₁-C₆-alkylthio, C₁-C6-alkylamino, di-C₁-C₆-alkylamino,            C₁-C₆-alkyl-aminocarbonyl, di-C₁-C₆-alkylaminocarbonyl,            C₁-C₆-alkylaminothiocarbonyl,            di-C₁-C₆-alkylamino-thiocarbonyl, C₂-C₆-alkenyl,            C₂-C₆-alkenyloxy, phenyl, phenoxy, benzyl, benzyloxy, 5- or            6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or            6-membered hetaryloxy, C(═NOR^(α)) —OR^(β)or            OC(R^(α))₂—C(R^(β))═NOR^(β),            -   where the cyclic groups for their part are unsubstituted                or substituted by one to three radicals R^(y):            -   R^(y) is cyano, nitro, halogen, hydroxyl, amino,                aminocarbonyl, aminothiocarbonyl, C₁-C₆-alkyl,                C₁-C₆-haloalkyl, C_(1-C) ₆-alkylsulfonyl,                C₁-C₆-alkyl-sulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy,                C₁-C₆-haloalkoxy, C₁-C₆-alkoxy-carbonyl,                C₁-C₆-alkylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino,                C₁-C₆-alkylaminocarbonyl, di-C₁-C₆-alkylaminocarbonyl,                C₁-C₆-alkylamino-thiocarbonyl,                di-C₁-C6-alkylaminothiocarbonyl, C₂-C₆-alkenyl,                C₂-C₆-alkenyloxy, C₃-C₆-cyclo-alkyl, C₃-C₆-cycloalkenyl,                phenyl, phenoxy, phenylthio, benzyl, benzyloxy, 5- or                6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or                6-membered hetaryloxy or C(═NOR^(α))-OR^(β);                -   R^(α),R^(β)are hydrogen or C₁-C₆-alkyl;        -   R^(a) and R^(b) together, via an alkylene or alkenylene            chain with the bridging atom, may also form a saturated or            unsaturated 5- or 6-membered ring;-   R³ is hydrogen, halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,    C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or C₃-C₈-alkenyloxy;-   R⁴ is hydrogen, halogen, cyano, hydroxyl, mercapto, azido,    C₁-C₆-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₆-haloalkyl,    C₁-C₆-alkoxy, C₃-C₈-alkenyloxy, C₃-C₈-alkynyloxy, C₁-C₆-haloalkoxy,    C₁-C₆-alkylthio, C₃-C₈-alkenylthio, C₃-C₈-alkynylthio,    C₁-C₆-haloalkylthio, —ON═CR^(a)R^(b), —CR^(c)═NOR^(a),    —NR^(c)N═CR^(a)R^(b), —NR^(a)R^(b), —NR^(c)NR^(a)R^(b), —NOR^(a),    —NR^(c)C(═NR^(c)′)NR^(a)R^(b), —NR^(c)C(═O)NR^(a)R^(b),    —NR^(a)C(═O)R^(c), —NR^(a)C(═NOR^(c))R^(c′), —OC(═O)R^(c),    —C(═NOR^(c))NR^(a)R^(b), —CR^(c)(═NNR^(a)R^(b)), —C(═O)NR^(a)R^(b)or    —C(═O)R^(c);    -   R^(c) is one of the monovalent groups mentioned under R^(a) and        R^(b);-   x is halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkyl; and-   m is an integer from 1 to 5.

Moreover, the invention relates to processes for preparing thesecompounds, to compositions comprising them and to their use forcontrolling harmful fungi.

Pyridylpyrimidine derivatives having fungicidal action are known fromEP-A 407 899, DE-A 42 27 811 and WO-A 92/10490. Tetrahydropyrimidinederivatives having fungicidal action are known from GB-A 2 277 090.

The compounds described in the abovementioned publications are suitablefor use as crop protection agents against harmful fungi.

However, in many cases their activity is unsatisfactory.

It is an object of the present invention to provide compounds havingimproved activity.

We have found that this object is achieved by the phenylpyrimidinederivatives I defined at the outset. Moreover, we have found processesfor their preparation and compositions comprising them for controllingharmful fungi and their use for this purpose.

Compared to the prior-art compounds, the compounds of the formula I haveincreased activity against harmful fungi.

The compounds I can be obtained by different routes.

To prepare compounds of the formula I in which R⁴ is cyano or a groupbound via a heteroatom, the starting materials used are advantageouslysulfones of the formula II. In the formula II, the substituents X_(m)and R¹ to R³ are as defined in formula I and R is C₁-C₄-alkyl,preferably methyl.

The sulfones of the formula II are reacted under basic conditions withcompounds of the formula III. For practical reasons, it is alternativelypossible to employ directly the alkali metal, alkaline earth metal orammonium salt of the compound III.

This reaction is usually carried out at temperatures of from 250° C. to250° C., preferably from 40° C. to 210° C., in an inert organic solventin the presence of a base [cf. DE-A 39 01 084; Chimia, 50, 525-530(1996); Khim. Geterotsikl. Soedin, 12 1696-1697(1998).

Suitable solvents are halogenated hydrocarbons, ethers, such as diethylether, diisopropyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane,dioxane, anisole and tetrahydrofuran, and also dimethyl sulfoxide,dimethylformamide and dimethylacetamide. Particular preference is givento ethanol, dichloromethane, acetonitrile and tetrahydrofuran. It isalso possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkalimetal and alkaline earth metal hydroxides, such as lithium hydroxide,sodium hydroxide, potassium hydroxide and calcium hydroxide, alkalimetal and alkaline earth metal hydrides, such as lithium hydride, sodiumhydride, potassium hydride and calcium hydride, and alkali metal andalkaline earth metal carbonates, such as lithium carbonate, potassiumcarbonate and calcium carbonate. The bases are generally employed incatalytic amounts; however, they can also be employed in excess.

The starting materials are generally reacted with one another inequimolar amounts. In terms of yield, it may be advantageous to employan up to 10-fold excess, in particular up to 3-fold excess, of III,based on II.

Compounds of the formula I in which R⁴ is hydrogen, alkyl, alkenyl,alkynyl or haloalkyl are advantageously obtained from phenylmalonicesters of the formula IV by reaction with amidines of the formula V.

This reaction is advantageously carried out under the conditions knownfrom J. Chem. Soc. (1943) 388 and J. Org. Chem. 17 (1952), 1320.

Phenylmalonic esters of the formula IV are known from EP-A 10 02 788.

Hydroxypyrimidines of the formula VI are converted into halogencompounds VII [cf. J. Chem. Soc. (1943) 383; Helv. Chim. Acta 64 (1981),113-152]. Suitable halogenating agents are in particular POCl₃ andPOBr₃.

The halopyrimidines VII give, by reaction with amines VIII, compounds ofthe formula I.

This reaction is advantageously carried out under J. Chem. Soc. (1943)383 and Chem. Eur. J. 5 (12) (1999), 3450-3458.

Phenylpyrimidines of the formula I in which R³ is cyano or a groupattached via oxygen are advantageously obtained from the correspondinghalogen compounds of the formula I by reaction with compounds IX underbasic conditions. For practical reasons, it is alternatively possible toemploy directly the alkali metal, alkaline earth metal or ammonium saltof the compound IX.

This reaction is usually carried out at temperatures of from 25° C. to250° C., preferably from 40° C. to 210° C., in an inert organic solvent,if appropriate in the presence of a base [cf. Recl. Trav. Chim. Pays-Bas61 (1942), 291; J. Heterocycl. Chem. 30 (4) (1993), 993-995].

Suitable solvents are ethers, sulfoxides, amides, particularlypreferably dimethyl sulfoxide, N,N-dimethylformamide,N-methylpyrrolidone, N,N-dimethylacetamide, diethyl ether,tetrahydrofuran and 1,2-dimethoxyethane. It is also possible to usemixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkalimetal and alkaline earth metal hydroxides, such as lithium hydroxide,sodium hydroxide, potassium hydroxide and calcium hydroxide, alkalimetal and alkaline earth metal hydrides, such as lithium hydride, sodiumhydride, potassium hydride and calcium hydride, and alkali metal andalkaline earth metal carbonates, such as lithium carbonate, potassiumcarbonate and calcium carbonate.

The bases are generally employed in catalytic amounts; however, they canalso be employed in excess.

Phenylpyrimidines of the formula I in which R³ is C₁-C₆-alkyl orC₁-C₆-haloalkyl are advantageously obtained from the correspondinghalogen compounds of the formula I by reaction with organometalliccompounds of the formula X in which M is a group Mg-Hal, Zn-R³ orB(OR)₂, where Hal is a halogen atom and R is hydrogen or C₁-C₄-alkyl andR³ is C₁-C₆-alkyl.

This reaction is usually carried out at temperatures of from -25° C. to250° C., preferably from 0° C. to 150° C., in an inert organic solvent,if appropriate in the presence of a transition metal catalyst [vgl.Chem. and Pharm. Bull. 28 (2) (1980), 571-577; Tetrahedron Lett. 37 (8)(1996), 1309; Tetrahedron Lett. 35 (19) (1994), 3155; Synlett 7 (1999),1145].

Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons andethers, particularly preferably diethyl ether, tetrahydrofuran,1,2-dimethoxyethane, benzene, toluene and xylene. It is also possible touse mixtures of the solvents mentioned.

Suitable transition metal catalysts are iron, cobalt, nickel, rhodium,platinum or palladium compounds, in particular nickel(0), nickel(II),palladium(0) and palladium(II) compounds. It is possible to use salts,such as palladium chloride or palladium acetate, or else Pd complexes.The only condition is that the palladium ligands can be replaced by thesubstrate under the reaction conditions.

The starting materials are generally reacted with one another inequimolar amounts. In terms of yield, it may be advantageous to employan up to 10-fold, in particular up to 3-fold, excess of X, based on I.

The starting materials of the formula II required for preparing thecompounds I can be obtained by methods known from the literature, forexample by the following synthesis route:starting from phenylmalonic acid alkyl esters of the formula XI andthiourea, compounds of the formula XII are obtained

where in formula XI R is C₁-C₆-alkyl. The reaction is usually carriedout in a protic solvent, such as, for example, an alcohol, in particularethanol, if appropriate in the presence of a base such as Na₂CO₃ orNaHCO₃. The reaction temperature is preferably 70-220° C. [cf. Collect.Czech. Chem. Commun. 48 (1983), 137-143; Heteroat. Chem. 10 (1999),17-23; Czech. Chem. Commun. 58 (1993), 2215-2221].

The required phenylmalonic acid esters XI are known from EP-A 10 02 788.

Using alkylating agents XIII, compounds XII are converted intothiobarbituric acid derivatives. In the formula XIII, R is C₁-C₆-alkyland X is a nucleophilically displaceable leaving group. Formula XIIIrepresents, in a general manner, customary alkylating agents, such asmethyl chloride and methyl bromide, dimethyl sulfate or methylmethanesulfonate.

The reaction can be carried out in water or else in a dipolar aproticsolvent, such as, for example, N,N-dimethylformamide [cf. U.S. Pat. No.5,250,689]; it is preferably carried out in the presence of a base, suchas, for example, KOH, NaOH, NaHCO₃ and Na₂CO₃ or pyridine. The reactiontemperature is preferably 10-60° C.

Compounds XIV are converted into dichloropyrimidines of the formula XV[cf. EP-A 745 593; WO-A 99/32458; J.Org. Chem. 58 (1993), 3785-3786].

Suitable chlorinating agents [Cl] are, for example, POCl₃, PCl₃/Cl₂ orPCl₅. The reaction can be carried out in excess chlorinating agent(POCl₃) or in an inert solvent. This reaction is usually carried out atfrom 10 to 180° C.

By amination with XVI, the dichloro compounds of the formula XV areconverted into the compounds of the formula XVII.

This reaction is preferably carried out at from 20 to 120° C. [cf. J.Chem. Res. S (7) (1995), 286-287; Liebigs Ann. Chem. (1995), 1703-1705]in an inert solvent, if appropriate in the presence of an auxiliarybase, such as NaHCO₃, Na₂CO₃ or tert.amines.

The amines of the formula XVI are commercially available or known fromthe literature, or they can be prepared by known methods.

The thio compounds XVII are oxidized to the sulfones of the formula II.

The reaction is preferably carried out at from 10 to 50° C. in thepresence of protic or aprotic solvents [cf.: B. Kor. Chem. Soc. 16(1995), 489-492; Z. Chem. 17 (1977), 63]. Suitable oxidizing agents are,for example, hydrogen peroxide or 3-chloroperbenzoic acid.

The introduction of groups R³ different from chlorine into the sulfonesII can be carried out analogously to the compounds of the formula I.

Compounds of the formula I in which R⁴ is —C(═O)R^(c),—C(═O)NR^(a)R^(b), —C(═NOR^(c))NR^(a)R^(b), —C(═NNR^(a)R^(b))R^(c) or—C(═NOR^(a))R^(c) are advantageously obtained from compounds of theformula I in which R⁴ is cyano.

Compounds of the formula I in which R⁴ is —C(═O)NR^(a)R^(b)or—C(═NOR^(c))NR^(a)R^(b)are from the corresponding nitriles (R⁴ ═cyano)by hydrolysis under acidic or basic conditions to give the carboxylicacids of the formula Ia and amidation with amines HNR^(a)R^(b).Hydrolysis is usually carried out in inert polar solvents, such as wateror alcohols, preferably using inorganic bases, such as alkali metal oralkaline earth metal hydroxides, in particular NaOH.

These conversions are advantageously carried out under the conditionsknown from Chem. and Pharm. Bull. 30(12) (1982), 4314.

Compounds of the formula I in which R⁴ is —C(═NOR^(c))NR^(a)R^(b)areobtained from amides of the formula Ib by oximation with substitutedhydroxylamines H₂N—OR^(c) under basic conditions [cf. U.S. Pat. No.4,876,252]. The substituted hydroxylamines can be used as free base or,preferably, in the form of their acid addition salts. Particularlysuitable are, for practical reasons, the halides, such as the chlorides,or the sulfates.

Alternatively, the amidoximes of the formula Ic in which R^(a) and R^(b)are hydrogen can also be obtained from the corresponding nitriles(R⁴=cyano) by reaction with hydroxylamine and subsequent alkylation.This reaction is advantageously carried out under the conditions knownfrom DE-A 198 37 794.

Compounds of the formula I in which R⁴ is —C(═O)R^(c) can be obtainedfrom the corresponding nitriles (R⁴=cyano) by reaction with Grignardreagents R^(c)-Mg-Hal where Hal is a halogen atom, in particularchlorine or bromine.

This reaction is advantageously carried out under the conditions knownfrom J. Heterocycl. Chem. 31(4) (1994), 1041.

The substituents and indices in formulae Ia, Ib and Ic correspond tothose in formula I.

Compounds of the formula I in which R⁴ is —C(═NNR^(a)R^(b))R^(c) can beobtained via the carbonyl compounds Id. They are obtained by reacting Idwith hydrazines H₂NNR^(a)R^(b), preferably under the conditions knownfrom J. Org. Chem. 31 (1966), 677.

Compounds of the formula I in which R⁴ is —C(═NOR^(a))R^(c) can beobtained by oximating carbonyl compounds Id. The oximation of Id iscarried out analogously to the oximation of the compounds Ib.

The reaction mixtures are worked up in a customary manner, for exampleby mixing with water, separating the phases and, if appropriate,chromatographic purification of the crude products. Some of theintermediates and end products are obtained in the form of colorless orslightly brownish, viscous oils which can be purified or freed fromvolatile components under reduced pressure and at moderately elevatedtemperature. If the intermediates and end products can be obtained assolids, purification can also be carried out by recrystallization ordigestion.

If individual compounds I are not obtainable by the routes describedabove, they can be prepared by derivatization of other compounds I.

In the definitions of the symbols given in the above formulae,collective terms were used which generally represent the followingsubstituents:

-   halogen: fluorine, chlorine, bromine and iodine;-   alkyl: saturated, straight-chain or branched hydrocarbon radicals    having 1 to 4 or 6 carbon atoms, for example C₁-C₆-alkyl such as    methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,    2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl,    2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,    hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,    2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,    1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,    2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,    1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl    and 1-ethyl-2-methylpropyl;-   haloalkyl: straight-chain or branched alkyl groups having 1 to 6    carbon atoms (as mentioned above), where in these groups some or all    of the hydrogen atoms can be replaced by halogen atoms as mentioned    above, for example C₁-C₂-haloalkyl such as chloromethyl,    bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,    difluoromethyl, trifluoromethyl, chlorofluoromethyl,    dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,    1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,    2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,    2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,    2,2,2-trichloroethyl and pentafluoroethyl;-   alkoxy: straight-chain or branched alkyl groups having 1 to 10    carbon atoms (as mentioned above) which are attached to the skeleton    via an oxygen atom (—O—);-   alkylthio: straight-chain or branched alkyl groups having 1 to 10 or    1 to 4 carbon atoms (as mentioned above) which are attached to the    skeleton via a sulfur atom (—S—);-   alkenyl: unsaturated, straight-chain or branched hydrocarbon    radicals having 2 to 4, 6 or 8 carbon atoms and a double bond in any    position, for example C₂-C₆-alkenyl such as ethenyl, 1-propenyl,    2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,    1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,    2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,    1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,    1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,    1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,    1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,    1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,    1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,    1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,    4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,    3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,    2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,    1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,    4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 30    1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl,    1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,    1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl,    1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,    2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,    2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl,    3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl,    1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl,    2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,    1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and    1-ethyl-2-methyl-2-propenyl;-   haloalkenyl: unsaturated, straight-chain or branched hydrocarbon    radicals having 2 to 8 carbon atoms and a double bond in any    position (as mentioned above), where in these groups some or all of    the hydrogen atoms may be replaced by halogen atoms as mentioned    above, in particular by fluorine, chlorine or bromine;-   alkynyl: straight-chain or branched hydrocarbon groups having 2 to    4, 6 or 8 carbon atoms and a triple bond in any position, for    example C₂-C6-alkynyl such as ethynyl, 1-propynyl, 2-propynyl,    1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,    2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,    1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,    1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,    3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,    1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,    2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,    4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,    1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,    2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,    1-ethyl-3-butynyl, 2-ethyl-3-butynyl and    1-ethyl-1-methyl-2-propynyl;-   haloalkynyl: unsaturated, straight-chain or branched hydrocarbon    radicals having 2 to 8 carbon atoms and a triple bond in any    position (as mentioned above), where in these groups some or all of    the hydrogen atoms may be replaced by halogen atoms as mentioned    above, in particular by fluorine, chlorine or bromine;-   alkynyloxy: unsaturated, straight-chain or branched hydrocarbon    radicals having 3 to 8 carbon atoms and a triple bond in any    position which is not adjacent to the heteroatom (as mentioned    above), which are attached to the skeleton via an oxygen atom (—O—);-   cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 6,    8 or 10 carbon ring members, for example C₃-C₈-cycloalkyl such as    cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and    cyclooctyl;-   5- or 6-membered heterocyclyl containing, in addition to carbon ring    members, one to three nitrogen atoms and/or one oxygen or sulfur    atom or one or two oxygen and/or sulfur atoms, for example    2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,    3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl,    3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,    3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl,    3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl,    4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl,    5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl,    1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl,    1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl,    1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thia-    diazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl,    2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl,    2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl,    2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl,    3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 5    3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl,    3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl,    3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl,    3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl,    3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl,    3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl,    2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl,    2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl,    3,4-dihydro-pyrazol-1-yl, 3,4-dihydropyrazol-3-yl,    3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl,    4,5-dihydropyrazol-1-yl, 4,5-dihydro- pyrazol-3-yl,    4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl,    2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl,    2,3-dihydro-oxazol-4-yl, 2,3-dihydrooxazol-5-yl,    3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,    3,4-dihydrooxazol-4-yl, 3,4-dihydro-oxazol-5-yl,    3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl,    3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl,    1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetra-hydropyranyl,    2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl,    2-hexahydropyrimidinyl, 4-hexahydro-pyrimidinyl,    5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexa-hydrotriazin-2-yl    and 1,2,4-hexahydrotriazin-3-yl;-   5- or 6-membered heteroaryl which, in addition to carbon ring    members, may contain heteroatoms from the group consisting of    oxygen, sulfur and nitrogen: aryl as mentioned above or mono- or    bicyclic heteroaryl, for example    -   5-membered heteroaryl which contains one to four nitrogen atoms        or one to three nitrogen atom and one sulfur or oxygen atom:        5-membered heteroaryl groups which, in addition to carbon atoms,        may contain one to four nitrogen atoms or one to three nitrogen        atoms and one sulfur or oxygen atom as ring members, for example        2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl,        3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,        4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl,        5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl,        4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,        1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,        1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,        1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl        and 1,3,4-triazol-2-yl;    -   benzo-fused 5-membered heteroaryl which contains one to three        nitrogen atoms or one nitrogen atom and one oxygen or sulfur        atom: 5-membered heteroaryl groups which, in addition to carbon        atoms, contain one to four nitrogen atoms or one.to three        nitrogen atoms and one sulfur or oxygen atom as ring members and        in which two adjacent carbon ring members or one nitrogen and        one adjacent carbon ring member may be bridged by a        buta-1,3-dien-1,4-diyl group;    -   6-membered heteroaryl which contains one to three or one to four        nitrogen atoms: 6-membered heteroaryl groups which, in addition        to carbon ring members, may contain one to three or one to four        nitrogen atoms as ring members, for example 2-pyridinyl,        3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,        2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,        1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl;-   alkylene: divalent unbranched chains of 1 to 4 CH₂ groups, for    example CH₂, CH₂CH₂, CH₂CH₂CH₂ and CH₂CH₂CH₂CH₂;-   oxyalkylene: divalent unbranched chains of 2 to 4 CH₂ groups, where    one valency is attached to the skeleton via an oxygen atom, for    example OCH₂CH₂, OCH₂CH₂CH₂ and OCH₂CH₂CH₂CH₂;-   oxyalkyleneoxy: divalent unbranched chains of 1 to 3 CH₂ groups,    where both valencies are attached to the skeleton via an oxygen    atom, for example OCH₂O, OCH₂CH₂O and OCH₂CH₂CH₂O;-   alkenylene: divalent unbranched chains of 1 to 3 CH₂ groups and one    CH═CH group in any position, for example CH═CHCH₂, CH₂CH═CHCH₂,    CH═CHCH₂CH₂, CH₂CH═CHCH₂CH₂ and CH═CHCH₂CH₂CH₂.

With a view to the intended use of the phenylpyrimidines of the formulaI, the following meanings of the substituents are particularlypreferred, in each case on their own or in combination:

Preference is given, in particular, to compounds I in which R¹ ishydrogen.

Particular preference is likewise given to compounds I in which R¹ andR² independently of one another are C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₃-C₆-cycloalkyl or C₂-C₆-alkenyl.

Particular preference is given to compounds of the formula I in which R¹is C₁-C₄-alkyl and R² is hydrogen.

Particular preference is given to compounds I in which R¹ and R²together with the bridging nitrogen atom form a saturated or unsaturated5- or 6-membered ring which may be interrupted by an ether (—O—), thio(—S—), sulfoxyl (—S[═O]—) or sulfonyl (—SO₂—) group and/or which may besubstituted by one or two methyl or halomethyl groups or in which twoadjacent carbon atoms are bridged by a methylene group. Substitution byone or two methyl or halomethyl groups, in particular one or two methylgroups, is particularly preferred.

Moreover, preference is given to compounds of the formula I in which R¹and R² together form a butylene, pentylene or a pentenylene chain whichmay be substituted by an alkyl group, in particular a methyl group or inwhich two adjacent carbon atoms may be bridged by a methylene group.

Preference is furthermore given to compounds of the formula I in whichR¹ and R² together form a pentylene or pentenylene chain which issubstituted by a methyl group.

Particular preference is given to compounds I in which R¹ and R²together with the bridging nitrogen atom form a 3- or4-methyl-piperidinyl group or a 2-methylpyrrolidine group.

In addition, particular preference is given to compounds I in which R³is halogen, in particular chlorine.

Particular preference is likewise given to compounds I in which R⁴ ishydrogen, cyano, azido, C₁-C₆-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl,C₁-C₆-haloalkyl, —ON═CR^(a)R^(b)or —NR^(c)N═CR^(a)R^(b)or —C (═NOR^(c))NR^(a)R^(b).

Particular preference is given to compounds I in which R⁴ is cyano,—CR^(a)NOR^(b) or —ON═CR^(a)R^(b), in particular −ON═CR^(a)R^(b).

In addition, preference is given to compounds I in which R⁴ is—NH(═NH)NHR^(c), —NHC(═O)NHR^(a), —NHC(═O)R^(a), —OC(═O)R^(a),—C(═NOR^(c))NH₂ or —CR^(c)(═NNR^(a)R^(b)).

Furthermore, preference is given to compounds I in which R⁴ is—NR^(c)N═CR^(a)R^(b).

Likewise, preference is given to compounds I in which R⁴ is—C(═NOR^(c))NR^(a)R^(b), in particular —C(═NOR^(c))NH₂.

In addition, particular preference is given to compounds I in which R⁴is C₁-C₆-alkenyl or azido.

Moreover, preference is given to compounds I in which R^(a) and R^(b)are identical or different and are hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy,phenyl or a five- or six-membered aromatic heterocycle, where the ringsmay be substituted by one to three groups R^(x); among these, particularpreference is given to the meanings hydrogen, alkyl, alkoxy andunsubstituted or substituted phenyl.

Particularly preferred embodiments of radicals R^(a) and R^(b) areC₁-C₄-alkyl, C₁-C₂-haloalkyl, C₁-C₄-alkoxy-C₁-C₂-alkyl, C₃-C₆-alkenyl,C₃-C₆-haloalkenyl, C₁-C₄-alkoxy, C₁-haloalkoxy, pyridyl, pyrazolyl,phenyl or benzyl, or R^(a) and R^(b) together form a butylene orpentylene chain, where the cyclic groups may be substituted by up tofour substituents selected from the group consisting of halogen,C₁-C₄-alkyl, C₁-haloalkyl, C₁-C₄-alkoxy and/or C₁-C₄-alkoxy-C_(1-C)₂-alkyl.

A preferred embodiment of R^(c) is hydrogen.

Preference is likewise given to compounds I in which X is chlorine,fluorine, methyl, trifluoromethyl or methoxy.

Moreover, particular preference is given to compounds I in which one ortwo substituents X are located in the position ortho to the point ofattachment of the pyrimidine ring.

In addition, particular preference is given to compounds IA

-   in which R¹ to R⁴ are as defined for formula I and X¹ to X⁵ are    identical or different and-   X¹ is fluorine, chlorine, C₁-C₄-alkyl, C₁-C₂-haloalkyl or    C₁-C₄-alkoxy; and-   X²,X³,X⁴,X⁵ are hydrogen or one of the groups mentioned under X¹.

Particular preference is given to compounds IA in which

-   X¹,x² are fluorine, chlorine, methyl, trifluoromethyl or methoxy;-   X³,X⁴,X⁵ are hydrogen or one of the groups mentioned under X¹ and    X².

Moreover, particular preference is given to compounds I in which X_(m),is F₅, 2-Cl, 2-F, 2-CH₃, 2-OCH₃, 2,6-Cl₂, 2,6-F₂, 2-Cl-6-F, 2-Br-6-F,2-CH₃-4-Cl, 2-CH₃-4-F, 2-CH₃-5-F, 2-CH₃-6-F, 2-CH₃-4-OCH₃, 2-CF₃-4-F,2-CF₃-5-F, 2-CF₃-6-F, 2-CF₃-4-OCH₃, 2-OCH₃ -6-F, 2,4,6-Cl₃, 2,3,6-F₃,2,4,6-F₃, 2,4,6-(CH₃)₃, 2,6-F₂ -4-CH₃, 2,6-F₂ -4-OCH₃, 2,4-F₂-6-OCH₃,2,6-(CH₃)₂-4-OCH₃ and 2,6-(CH₃)₂-4-F.

Particular preference is given to compounds I in which X_(m) is F₅,2,6-Cl₂, 2,6-F₂, 2-Cl-6-F, 2-CH₃-4-F, 2-CH₃-6-F, 2-CH₃-4-Cl and2,4,6-F₃.

The compounds I are suitable for use as fungicides. They haveoutstanding activity against a broad spectrum of phytopathogenic fungi,in particular from the class of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomycetes. Some of them act systemically, and theycan be employed in crop protection as foliar- and soil-actingfungicides.

They are especially important for controlling a large number of fungi ona variety of crop plants such as wheat, rye, barley, oats, rice, maize,grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruitspecies, ornamentals and vegetables such as cucumbers, beans, tomatoes,potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plantdiseases:

-   -   Alternaria species, Podosphaera species, Sclerotinia species,        Physalospora canker on vegetables and fruit,    -   Botrytis cinerea (gray mold) on strawberries, vegetables,        ornamentals and grapevines,    -   Corynespora cassiicola on cucumbers,    -   Colletotrichum species on fruit and vegetables,    -   Diplocarpon rosae on roses,    -   Elsinoe fawcetti and diaporthe citri on citrus fruits,    -   Sphaerotheca species on cucurbits, strawberries and roses,    -   Cercospora species on groundnuts, sugar beet and aubergines,    -   Erysiphe cichoracearum on cucurbits,    -   Leveillula taurica on peppers, tomatoes and aubergines,    -   Mycosphaerella species on apples and Japanese apricots,    -   Gymnosporangium yamadae, Leptothyrium pomi, Podosphaera        leucotricha and Gloedes pomigena on apples,    -   Cladosporium carpophilum on pears and Japanese apricots,    -   Phomopsis species on pears,    -   Phytophthora species on citrus fruits, potatoes, onions, in        particular Phytophthora infestans on potatoes and tomatoes,    -   Blumeria graminis (powdery mildew) on cereals,    -   Fusarium and Verticillium species on various plants,    -   Glomerella cingulata on tea,    -   Drechslera and Bipolaris species on cereals and rice,    -   Mycosphaerella species on bananas and groundnuts,    -   Plasmopara viticola on grapevines,    -   Personospora species on onions, spinach and chrysanthemums,    -   Phaeoisariopsis vitis and Spaceloma ampelina on grapefruits,    -   Pseudocercosporella herpotrichoides on wheat and barley,    -   Pseudoperonospora species on hops and cucumbers,    -   Puccinia species and Typhula species on cereals and lawn,    -   Pyricularia oryzae on rice,    -   Rhizoctonia species on cotton, rice and lawn,    -   Stagonospora nodorum and Septoria tritici on wheat,    -   Uncinula necator on grapevines,    -   Ustilago species on cereals and sugar cane, and also    -   Venturia species (scab) on apples and pears.

Moreover, the compounds I are suitable for controlling harmful fungisuch as Paecilomyces variotii in the protection of materials (e.g. wood,paper, paint dispersions, fibers and fabrics) and in the protection ofstored products.

The compounds I are applied by treating the fungi or the plants, seeds,materials or the soil to be protected against fungal infection, with afungicidally active amount of the active compounds. Application can beeffected both before and after infection of the materials, plants orseeds by the fungi.

In general, the fungicidal compositions comprise from 0.1 to 95,preferably 0.5 to 90, % by weight of active compound.

When used in crop protection, the rates of application are from 0.01 to2.0 kg of active compound per ha, depending on the nature of the desiredeffect.

In the treatment of seed, amounts of active compound of from 0.001 to0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram ofseed.

When used in the protection of materials or stored products, the rate ofapplication of active compound depends on the nature of the field ofapplication and on the desired effect. Rates of applicationconventionally used in the protection of materials are, for example,from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound percubic meter of material treated.

The compounds I can be converted into the customary formulations, e.g.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form depends on the particular purpose; in any case, it shouldensure a fine and uniform distribution of the compound according to theinvention.

The formulations are prepared in a known manner, e.g. by extending theactive compound with solvents and/or carriers, if desired usingemulsifiers and dispersants, it also being possible to use other organicsolvents as auxiliary solvents if the diluent used is water. Auxiliarieswhich are suitable are essentially: solvents such as aromatics (e.g.xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g.mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g.cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water;carriers such as ground natural minerals (e.g. kaolins, clays, talc,chalk) and ground synthetic minerals (e.g. highly disperse silica,silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g.polyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates) and dispersants such as lignosulfite waste liquors andmethylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids andtheir alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ether, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof napthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ether,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing orconcomitantly grinding the active substances with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active compounds to solidcarriers. Examples of solid carriers are mineral earths, such assilicas, silica gels, silicates, talc, kaolin, attaclay, limestone,lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calciumsulfate, magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders and othersolid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compound. The activecompounds are in this case employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are exemplary formulations:

-   I. 5 parts by weight of a compound according to the invention are    mixed intimately with 95 parts by weight of finely divided kaolin.    This gives a dust which comprises 5% by weight of the active    compound.-   II. 30 parts by weight of a compound according to the invention are    mixed intimately with a mixture of 92 parts by weight of pulverulent    silica gel and 8 parts by weight of paraffin oil which had been    sprayed onto the surface of this silica gel.

This gives a formulation of the active compound with good adhesionproperties (comprises 23% by weight of active compound).

-   III. 10 parts by weight of a compound according to the invention are    dissolved in a mixture composed of 90 parts by weight of xylene, 6    parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1    mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium    dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40    mol of ethylene oxide and 1 mol of castor oil (comprises 9% by    weight of active compound).-   IV. 20 parts by weight of a compound according to the invention are    dissolved in a mixture composed of 60 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight    of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol    and 5 parts by weight of the adduct of 40 mol of ethylene oxide and    1 mol of castor oil (comprises 16% by weight of active compound).-   V. 80 parts by weight of a compound according to the invention are    mixed thoroughly with 3 parts by weight of sodium    diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the    sodium salt of a lignosulfonic acid from a sulfite waste liquor and    7 parts by weight of pulverulent silica gel, and the mixture is    ground in a hammer mill (comprises 80% by weight of active    compound).-   VI. 90 parts by weight of a compound according to the invention are    mixed with 10 parts by weight of N-methyl-α-pyrrolidone, which gives    a solution which is suitable for use in the form of microdrops    (comprises 90% by weight of active compound).-   VII. 20 parts by weight of a compound according to the invention are    dissolved in a mixture composed of 40 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight    of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol    and 10 parts by weight of the adduct of 40 mol of ethylene oxide and    1 mol of castor oil. Pouring the solution into 100,000 parts by    weight of water and finely distributing it therein gives an aqueous    dispersion which comprises 0.02% by weight of the active compound.-   VIII. 20 parts by weight of a compound according to the invention    are mixed thoroughly with 3 parts by weight of sodium    diisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium    salt of a lignosulfonic acid from a sulfite waste liquor and 60    parts by weight of pulverulent silica gel, and the mixture is ground    in a hammer mill. Finely distributing the mixture in 20,000 parts by    weight of water gives a spray mixture which comprises 0.1% by weight    of the active compound.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, e.g. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, spreading orpouring. The use forms depend entirely on the intended purposes; in anycase, they are intended to guarantee the finest possible distribution ofthe active compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates,pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances as suchor dissolved in an oil or solvent can be homogenized in water by meansof wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within substantial ranges. In general, they are from 0.0001 to10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active compound, or even the activecompound without additives.

Various types of oils, herbicides, fungicides, other pesticides, orbactericides may be added to the active compounds, if appropriate alsojust prior to use (tank mix). These agents can be admixed with theagents according to the invention in a weight ratio of 1:10 to 10:1.

In the use form as fungicides, the compositions according to theinvention can also be present together with other active compounds, e.g.with herbicides, insecticides, growth regulators, fungicides or elsewith fertilizers. Mixing the compounds I or the compositions comprisingthem in the use form as fungicides with other fungicides frequentlyresults in a broader fungicidal spectrum of action.

The following list of fungicides, together with which the compoundsaccording to the invention can be used, is intended to illustrate thepossible combinations, but not to impose any limitation:

-   -   sulfur, dithiocarbamates and their derivatives, such as        iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate,        zinc ethylenebisdithiocarbamate, manganese        ethylenebisdithiocarbamate, manganese zinc        ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide,        ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),        ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc        (N,N′-propylenebisdithiocarbamate),        N,N′-polypropylene-bis(thiocarbamoyl)disulfide;    -   nitro derivatives, such as dinitro(1-methylheptyl)phenyl        crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,        2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl        5-nitroisophthalate;    -   heterocyclic substances, such as 2-heptadecyl-2-imidazoline        acetate, 2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide,        2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl        phthalimidophosphonothioate,        5-amino-1-[bis(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,        2,3-dicyano-1,4-dithioanthraquinone,        2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl        1-(butylcarbamoyl)-2-benzimidazolecarbamate,        2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole,        2-(4-thiazolyl)-benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,        N-trichloromethylthiotetrahydrophthalimide,        N-trichloromethylthiophthalimide,    -   N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfodiamide,        5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,        2-thiocyanato-methylthiobenzothiazole,        1,4-dichloro-2,5-dimethoxybenzene,        4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,        pyridine-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt,        2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,        2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,        2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,        2-methylfuran-3-carboxanilide,        2,5-dimethylfuran-3-carboxanilide,        2,4,5-trimethylfuran-3-carboxanilide,        cyclohexyl-2,5-dimethylfuran-3-carboxamide,        N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,        2-methylbenzanilide, 2-iodobenzanilide,        N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,        piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,        1-(3,4-dichloroanilino)-i-formylamino-2,2,2-trichloroethane,        2,6-dimethyl-N-tridecylmorpholine or its salts,        2,6-dimethyl-N-cyclododecylmorpholine or its salts,        N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,        N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine,        1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,        1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole,        N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea,        1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,        1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,        (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,        α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,        5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,        bis(p-chlorophenyl)-3-pyridinemethanol,        1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,        1,2-bis-(3-methoxycarbonyl-2-thioureido)benzene,    -   strobilurins such as methyl        E-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylates,        (E)-2-(methoxyimino)-N-methyl-2-[α-(2,5-xylyloxy)-o-tolyl]acetamide,        {2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanone        O-methyloxime, methyl        (E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate,        (E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide,        (2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-2,8-dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamide,        methyl        (E)-3-methoxy-2-{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylate,        methyl        N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}-(N-methoxy)carbamate,        methyl        (E)-methoxyimino-{(E)-α-[1-(α,α,α-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate,    -   anilinopyrimidines such as        N-(4,6-dimethylpyrimidin-2-yl)-aniline,        N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,        N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,    -   phenylpyrroles such as        4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,    -   cinnamides such as        3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine,        3-(4-fluorophenyl)-3-(3,4-dimethozyphenyl)acryloylmorpholide,    -   and a variety of fungicides such as dodecylguanidine acetate,        1-(3-bromo-6-methoxy-2-methylphenyl)-1-(2,3,4-trimethoxy-6-methylphenyl)methanone,        3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,        hexachlorobenzene, methyl        N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,        DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alanine methyl        ester,        N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino-butyrolactone,        DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanine methyl ester,        5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,        3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,        3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,        N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,        2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,        1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,        2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,        N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,        1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole-5-chloro-2-cyano-4-n-tolylimidazole-1-sulfodimethylamide,        3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide.

SYNTHESIS EXAMPLES

With due modification of the starting compounds, the protocols shown inthe synthesis examples below were used for obtaining further compoundsI. The resulting compounds, together with physical data, are listed inTable 1 below.

Example 1 Preparation of[6-chloro-2-(N′-isopropylidene-hydrazino)-5-(2,4,6-trifluorophenyl)pyrimidine-4-yl]-((S)-1-tri-fluoromethylethyl)amine[I-1]

0.16 g (2.2 mmol) of acetone oxime was added to 0.065 g (2.4 mmol) ofsodium hydride in 10 ml of dimethylformamide (DMF). The mixture wasstirred at 20-25° C. for 1 hour, after which 1.0 g (2.2 mmol) of[6-chloro-2-methanesulfonyl-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine(abbr. sulfone 1) was added. After a further 14 hours of stirring at20-25° C., the mixture was poured into water and extracted withdichloromethane. The combined organic phases were washed with water,then dried and finally freed from the solvent. This gave 0.6 g of thetitle compound of m.p. 157-159° C.

Example 2 Preparation of[6-chloro-2-methoxy-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine[I-24]

294 mg (1.30 mmol) of sodium methoxide (90% in methanol) were added to asolution of 282 mg (0.65 mmol) of sulfone 1 in 4 ml of anhydrous DMF.The mixture was stirred at 20-25° C. for 16 hours and then diluted withMTBE, washed with water and dried. Distillative removal of the solventand chromatography on silica gel gave 0.14 g of the title compound ofm.p. 121-129° C.

Example 3 Preparation of[6-chloro-2-methylsulfanyl-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]isopropylamine[I-30]

70 mg (1.0 mmol) of sodium thiomethoxide, dissolved in 3 ml of anhydrousTHF, were added to a solution of 216 mg (0.5 mmol) of[6-chloro-2-methanesulfonyl-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]isopropylamine(abbr. sulfone 2) in 2 ml of anhydrous DMF. The mixture was stirred at20-25° C. for 16 hours and then diluted with MTBE, washed with water anddried. Distillative removal of the solvent and chromatography on silicagel gave 0.21 g of the title compound of m.p. 112-116° C.

Example 4 Preparation of[6-chloro-2-hydrazino-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine

An ethanolic solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.13 g (2.54mmol) of hydrazine hydrate was stirred at 20-25° C. for 2 hours. Thesolvent was distilled off and the residue was digested with diisopropylether, and the residue was then filtered off and washed with diisopropylether/hexane 1:1.

Example 5 Preparation of[6-chloro-2-[N′-(1-trifluoromethylethylidene)hydrazino]-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine[I-56]

A solution of 0.8 g (2.07 mmol) of the hydrazide from Ex. 4 and 0.28 g(2.49 mmol) of 1,1,1-trifluoroacetone in acetonitrile was stirred at20-25° C. for 16 hours. The precipitate was filtered off; the filtrategave, after chromatography on silica gel (CH:MTBE 95:5), 0.3 g of thetitle compound of m.p. 205-207° C.

Example 6 Preparation of[6-chloro-2-(N-phenylhydrazino)-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine[I-62]

An ethanolic solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.15 g (1.38mmol) of phenylhydrazine was refluxed for 14 hours. Cooling,distillative removal of the solvent and chromatography on silica gel(cyclohexane:methyl tert-butyl ether [MTBE] 95:5) gave 0.36 g of thetitle compound.

Example 7 Preparation of[2-azido-6-chloro-5-(2,4,6-trifluorophenyl)pyrimidin-4-yl]-((S)-1-trifluoromethylethyl)amine[I-66]

A solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.11 g (1.62 mmol) ofsodium azide in acetonitrile was refluxed for 2 hours. Cooling,distillative removal of the solvent and digestion of the residue withwater gave 0.33 g of the title compound of m.p. 152-154° C.

Example 8 Preparation of6-chloro-5-(2-chloro-6-fluorophenyl)-N¹-isopropyl-N²-phenylpyrimidine-2,4-diamine[I-69]

At −70° C., 0.62 g (6.6 mmol) of aniline was added to a suspension of2.9 g of butyllithium (15% solution in hexane) in 15 ml oftetrahydrofuran [THF], and the mixture was then stirred at −70° C. for 1hour. 1.0 g (2.64 mmol) of[6-chloro-5-(2-chloro-6-fluorophenyl)-2-methanesulfonylpyrimidin-4-yl]isopropylamine(abbr. sulfone 3) was added, and the mixture was then warmed to 20-25°C. The reaction mixture was poured into ice-water and acidified withhydrochloric acid. The mixture was extracted with 2×40 ml of MTBE, andthe combined organic phases gave, after drying and distillative removalof the solvent, 1.0 g of the title compound.

Example 9 Preparation of4-chloro-6-((S)-1-trifluoromethylethyl-amino)-5-(2,4,6-trifluorophenyl)pyrimidin-2-carbonitrile[I-73]

A solution of 0.5 g (1.15 mmol) of sulfone 1 and 0.36 g (2.31 mmol) oftetraethylammonium cyanide in dichloromethane was stirred at 20-25° C.for 20 hours. Distillative removal of the solvent and chromatography onsilica gel (cyclohexane [CH]:MTBE 9:1) gave 0.18 g of the title compoundof m.p. 134-136° C.

Example 10 Preparation of4-chloro-5-(2-chloro-6-fluorophenyl)-6-isopropylaminopyrimidine-2-carbonitrile[I-74]

A solution of 1.0 g (2.63 mmol) of sulfone 3 and 0.21 g (3.16 mmol) ofpotassium cyanide in acetonitrile was stirred at 20-25° C. for 5 days.The solvent was distilled off and the residue was digested withMTBE:ethyl acetate [EA] 9:1. Filtration and concentration of thefiltrate gave 0.61 g of the title compound of m.p 186-188° C. TABLE I

Phys. data No. R¹ R² R³ R⁴ X¹ X² X³ X⁴ X⁵ (m.p. [° C.]) I-1

H Cl

F F H F H 157-159 I-2

H Cl

F F H F H 88-92 I-3

H Cl

F F H F H 176-179 I-4

H Cl

F F H F H 151-155 I-5

H Cl

F F H F H 110-112 I-6

H Cl

F F H F H 145-146 I-7

H Cl

F F H F H 139-141 I-8

H Cl

F F H F H 350 I-9

H Cl

F F H F H 84-86 I-10

H Cl

F F H F H 68-70 I-11

H Cl

F F H F H 87-90 I-12

H Cl

F F H F H 137-139 I-13

H Cl

Cl F H H H 147-149 I-14

H Cl

F F H F H oil I-15

H Cl

Cl F H H H 165-168 I-16

H Cl

F F H F H oil I-17

H Cl

Cl F H H H 110-112 I-18

H Cl

Cl F H H H 125-127 I-19

H Cl

F F H F H 116-117 I-20

H Cl

Cl F H H H  98-100 I-21

H Cl

Cl F H H H 118-121 I-22

H Cl

Cl F H H H 108-111 I-23

H Cl

F F H F H 129-131 I-24

H Cl

F F H F H 121-129 I-25

H Cl

F F H F H 147-149 I-26

H Cl

F F H F H 159-161 I-27

Cl

Cl F H H H 164-169 I-28

Cl

F F H F H oil I-29

Cl

F F H F H oil I-30

H Cl

F F H F H 112-116 I-31

H Cl

Cl F H H H 106-110 I-32

H Cl

F F H F H oil I-33

H Cl

Cl F H H H 104-108 I-34

H Cl

F F H F H 95-98 I-35

H Cl

Cl F H H H oil I-36

H Cl

F F H F H oil I-37

H Cl

Cl F H H H 111-113 I-38

H Cl

Cl F H H H oil I-39

H Cl

Cl F H H H 94-96 I-40

H Cl

F F H F H oil I-41

H Cl

Cl F H H H 114-117 I-42

H Cl

F F H F H oil I-43

H Cl

F F H F H 68-69 I-44

H Cl

F F H F H 73-76 I-45

H Cl

F F H F H oil I-46

H Cl

F F H F H oil I-47

H Cl

F F H F H 64-65 I-48

H Cl

F H H H H 124-126 I-49

Cl

F H H H H oil I-50

Cl

F H H H H oil I-51

H Cl

F H H H H oil I-52

Cl

F H H H H oil I-53

H Cl

F H H H H 135-137 I-54

H Cl

F F H F H oil I-55

H Cl

F F H F H oil I-56

H Cl

F F H F H 205-207 I-57

H Cl

F F H F H 185-187 I-58

H Cl

F F H F H 84-87 I-59

H Cl

F F H F H 138-140 I-60

H Cl

F F H F H 205-208 I-61

H Cl

F F H F H 152-155 I-62

H Cl

F F H F H oil I-63

H Cl

F F H F H 132-134 I-64

H Cl

F F H F H 126-128 I-65

H Cl

F F H F H oil I-66

H Cl

F F H F H 152-154 I-67

H Cl

Cl F H H H 91-94 I-68

H Cl

Cl F H H H 151-153 I-69

H Cl

Cl F H H H oil I-70

H Cl

Cl F H H H oil I-71

Cl

Cl F H H H 107-109 I-72

Cl

Cl F H H H oil I-73

H Cl

F F H F H 134-136 I-74

H Cl

Cl F H H H 186-188 I-75

H Cl

F F H F H 83-85 I-76

H Cl

Cl F H H H 87-90 I-77

CH₃ Cl

H H F H H 75-77 I-78

Cl

Cl F H H H oil I-79

Cl

Cl F H H H oil I-80

Cl

Cl F H H H oil I-81

H Cl

F F H F H 94-96 I-82

H Cl

F F H F H  91 I-83

H Cl

F F H F H 180 I-84

H Cl

F F H F H 157 I-85

H Cl

F F H F H 159 I-86

H Cl

F F H F H 113-118 I-87

H Cl

F F H OCH₃ H oil I-88

Cl

F F H F H oil I-89

Cl

F F H F H oil I-90

Cl

F F H F H oil I-91

Cl

F F H F H oil I-92

Cl

Cl F H H H oil I-93

Cl

F H H CH₃ H oil I-94

Cl

CH₃ H H CH₃ H oil I-95

H Cl

F F H F H  99-105 I-96

H Cl

F F H F H 120-123 I-97

H Cl

F F H F H 106-109 I-98

H Cl

F F H F H 120-123 I-99

H Cl —OH F F H F H  84-101 I-100

H Cl

F F H F H 156-158 I-101

H Cl

F F H F H oil I-102

H Cl

Cl F H H H oil I-103

H Cl

Cl F H H H oil I-104

H Cl

Cl F H H H oil I-105

H Cl

Cl F H H H oil I-106

H Cl

Cl F H H H oil I-107

H Cl

Cl H H F H 127 I-108

H Cl

F F H OCH₃ oil I-109

Cl

F F H F H  98-102 I-110

Cl

F F H F H oil I-111

Cl

F F H F H oil I-112

Cl

F F H F H oil I-113

Cl

F F H F H 123-125 I-114

H Cl

F F H F H 133 I-115

H Cl

F F H F H 155 I-116

H Cl

F F H F H 146 I-117

H Cl

F F H F H 126-129 I-118

Cl

F F H F H oil I-119

Cl

F F H F H oil I-120

Cl

F F H F H oil I-121

Cl

F F H F H 107-109 I-122

Cl

F F H F H oil I-123

Cl

F F H F H 141-149 I-124

Cl

F F H F H 179-188 I-125

Cl

F F H F H 181-191 I-126

Cl

F F H F H oil I-127

Cl

F F H F H oil I-128

Cl

F F H F H oil I-129

Cl

F F H F H oil I-130

Cl CN F F H F H 89-98 I-131

Cl

F F H F H 82-90 I-132

Cl

F F H F H oil I-133

Cl

F F H F H oil I-134

Cl

F F H F H oil I-135

Cl

F F H F H  96 I-136

Cl

F F H F H  72 I-137

Cl

F F H F H 125 I-138

Cl

F F H F H 119 I-139

Cl

F F H F H 154 I-140

Cl

CH₃ CH₃ H H H oil I-141

Cl

F F H F H  98-102 I-142

CH₃

F F H F H oil I-143

Cl

F F H F H oil I-144

Cl

F F H F H oil I-145

Cl

F F H F H oil I-146

Cl

F F H F H  70 I-147

Cl

F F H F H oil I-148

Cl

F F H F H  96 I-149

Cl

F F H F H 128 I-150

OCH₃

F F H F H oil I-151

OCH₃

CH₃ H H F H 105 I-152

OCH₃

F F H F H oil I-153

OCH₃

F F H F H oil I-154

OCH₃

F F H F H oil I-155

OCH₃

F H H F H oil I-156

Cl

F F H F H 239-242 I-157

Cl

F F H F H oil I-158

Cl

F F H F H oil I-159

OCH₃

F F H F H 106-124 I-160

Cl

F F H F H oil I-161

Cl

F F H F H oil I-162

Cl

F F H F H 117 I-163

Cl

F F H F H oil I-164

Cl

F F H F H oil I-165

Cl

F F H F H oil I-166

Cl

F F H F H oil I-167

Cl

F F H F H oil I-168

Cl

F F H F H oil I-169

Cl

F F H F H oil I-170

Cl

F F H F H oil I-171

Cl

F F H F H oil I-172

Cl

F F H F H oil I-173

Cl

F F H F H oil I-174

Cl

F F H F H oil I-175

Cl

F F H F H oil I-176

Cl

F F H F H oil I-177

Cl

F F H F H oil I-178

Cl

F F H F H oil I-179

Cl

F F H F H oil I-180

Cl

F F H F H oil I-181

Cl

F F H F H oil I-182

Cl

F F H F H oil I-183

Cl

F F H F H oil I-184

Cl

F F H F H oil I-185

Cl

F F H F H oil I-186

Cl

F F H F H oil I-187

Cl

F F H F H oil I-188

Cl

CH₃ CH₃ H H H oil I-189

Cl

F F H OCH₃ H oil I-190

Cl

F F H OCH₃ H oil I-191

Cl

F F H OCH₃ H oil I-192

Cl

F F H OCH₃ H oil I-193

Cl

F F H OCH₃ H oil I-194

Cl

Cl F H H H 109 I-195

Cl

Cl F H H H oil I-196

Cl

Cl F H H H oil I-197

Cl

Cl F H H H 126 I-198

Cl

Cl F H H H 164-169 I-199

Cl

Cl F H H H oil I-200

Cl

Cl F H H H oil I-201

Cl

Cl F H H H 107-109 I-202

Cl

Cl F H H H oil I-203

Cl

Cl F H H H oil I-204

Cl

Cl F H H H oil I-205

Cl

Cl F H H H oil I-206

Cl

Cl F H H H oil I-207

Cl

F H H H H oil I-208

Cl

F H H CH₃ H oil I-209

Cl

F H H CH₃ H 136 I-210

Cl

F H H CH₃ H oil I-211

Cl

F H H CH₃ H 95-97 I-212

OCH₃

F H H CH₃ H oil I-213

Cl

F H H CH₃ H oil I-214

Cl

F H H CH₃ H oil I-215

Cl

F H H CH₃ H 148 I-216

Cl

F H H H H oil I-217

Cl

F H H H H oil I-218

Cl

H H F H H 75-77 I-219

H Cl

F F H F H 205-207 I-220

H Cl

F F H F H 185-187 I-221

H Cl

F F H F H 84-87 I-222

H Cl

F F H F H 138-140 I-223

H Cl

F F H F H oil I-224

H Cl

F F H F H 137-139 I-225

H Cl

F F H F H oil I-226

H Cl

F F H F H oil I-227

H Cl

F F H F H oil I-228

H Cl

F F H F H 112-116 I-229

H Cl

F F H F H oil I-230

H Cl

F F H F H 95-98 I-231

H Cl

Cl F H H H 91-94 I-232

H Cl

Cl F H H H 151-153 I-233

H Cl

Cl F H H H oil I-234

H Cl

Cl F H H H oil I-235

H Cl

Cl F H H H 147-149 I-236

H Cl

Cl F H H H 165-168 I-237

H Cl

Cl F H H H 110-112 I-238

H Cl

Cl F H H H 125-127 I-239

H Cl

Cl F H H H 118-121 I-240

H Cl

Cl F H H H  98-100 I-241

H Cl

Cl F H H H 108-111 I-242

H Cl

Cl F H H H 106-110 I-243

H Cl

Cl F H H H oil I-244

H Cl

Cl F H H H 111-113 I-245

H Cl

Cl F H H H 94-96 I-246

H Cl

Cl F H H H oil I-247

H Cl

Cl F H H H 114-117 I-248

H Cl

Cl F H H H 104-108 I-249

H Cl

Cl F H H H 186-188 I-250

H Cl

F H H H H oil I-251

H Cl

F H H H H 124-126 I-252

H Cl

F H H H H 135-137 I-253

H Cl

F F H F H 139-141 I-254

H Cl

F F H F H 157-159 I-255

H Cl

F F H F H 88-92 I-256

H Cl

F F H F H 176-179 I-257

H Cl

F F H F H 110-112 I-258

H Cl

F F H F H 350 I-259

H Cl

F F H F H 68-70 I-260

H Cl

F F H F H 145-146 I-261

H Cl

F F H F H 151-155 I-262

H Cl

F F H F H 87-90 I-263

H Cl

F F H F H 84-86 I-264

H Cl

F F H F H oil I-265

H Cl

F F H F H oil I-266

H Cl

F F H F H 152-155 I-267

H Cl

F F H F H 205-208 I-268

H Cl

F F H F H oil I-269

H Cl

F F H F H oil I-270

H Cl

F F H F H 132-134 I-271

H Cl

F F H F H 126-128 I-272

H Cl

F F H F H oil I-273

H Cl

F F H F H 152-154 I-274

H Cl

F F H F H 137-146 I-275

H Cl

F F H F H 121-129 I-276

H Cl

F F H F H 147-149 I-277

H Cl

F F H F H 159-161 I-278

H Cl

F F H F H 116-117 I-279

H Cl

F F H F H 129-131 I-280

H Cl

F F H F H oil I-281

H Cl

F F H F H 68-69 I-282

H Cl

F F H F H 73-76 I-283

H Cl

F F H F H oil I-284

H Cl

F F H F H oil I-285

H Cl

F F H F H 64-65 I-286

H Cl

F F H F H 83-85 I-287

H Cl

F F H F H 134-136 I-288

H Cl

Cl F H H H 87-90 I-289

H Cl

F F H F H  82 I-290

H Cl

F F H F H 130 I-291

H Cl

F F H F H  69 I-292

H Cl

F F H F H 120 I-293

H Cl

F F H F H  87 I-294

H Cl

F F H F H  97 I-295

H Cl

F F H F H 140 I-296

H Cl

F F H F H 175 I-297

H Cl

F F H F H 157 I-298

H Cl

F F H F H oil I-299

H Cl

F F H F H 108-112The R⁴ groups are attached to the pyrimidine skeleton via the freevalencies.Owing to their C═C, C═N and N═N double bonds, the groups R⁴ can bepresent as E/Z isomer mixtures.

EXAMPLES OF THE ACTIVITY AGAINST HARMFUL FUNGI

The fungicidal activity of the compounds of the formula I wasdemonstrated by the following experiments:

The active compounds were formulated, separately or together, as a 10%strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% byweight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifyingand dispersing action based on ethoxylated alkylphenols) and 10% byweight of Wettol® EM (nonionic emulsifier based on ethoxylated castoroil) and diluted with water to the desired concentration.

Use Example 1 Activity against Septoria Leaf Blotch of Wheat (Septoriatritici)

Leaves of potted wheat seedlings of the cultiva “Riband” were sprayed torunoff point with an aqueous preparation of active compound which hadbeen prepared from a stock solution comprising 10% of active compound,85% of cyclohexanone and 5% of emulsifier. 24 hours after the spraycoating had dried on, the seedlings were inoculated with an aqueousspore suspension of Septoria tritici. The suspension contained 2.0×10⁶spores/ml. The test plants were then placed in a greenhouse attemperatures between 18 and 22° C. and a relative atmospheric humidityclose to 100%. After 2 weeks, the extent of the development of thedisease was determined visually in % infection of the total leaf area.

In this test, the plants which had been treated with 250 ppm of theactive compounds Nos. 1, 12 to 15, 18, 19, 21, 24 to 26, 30, 32, 33, 54,55, 60, 61 to 65, 86, 160, 223, 224, 226, 228, 235 to 239, 248, 254,264, 265, 269, 270, 271, 272 and 275 to 278 of Table I showed aninfection of at most 7%, whereas the untreated plants were 90% infected.

Use Example 2 Activity against Net Blotch of Barley (Pyrenophora teres)

Leaves of potted barley seedlings of the cultivar “Igri” were sprayed torunoff point with an aqueous preparation of active compound which hadbeen prepared from a stock solution comprising 10% of active compound,85% of cyclohexanone and 5% of emulsifier and, 24 hours after the spraycoating had dried on, inoculated with an aqueous spore suspension ofPyrenophora [syn. Drechslera] teres, the net blotch pathogen. The testplants were then placed in a greenhouse at temperatures between 20 and24° C. and at 95-100% relative atmospheric humidity. After 6 days, theextent of the development of the disease was determined visually in %infection of the total leaf area.

In this test, the plants which had been treated with 250 ppm of theactive compounds Nos. 1, 55, 60, 64, 73, 88, 130, 134, 160, 163, 165,168, 171, 185, 186, 254, 255, 265, 267, 271, 274, 276, 277, 278 and 287of Table I showed an infection of not more than 15%, whereas theuntreated plants were 100% infected.

Use Example 3 Protective Activity against Mildew of Cucumber Caused bySphaerotheca fuliginea

Leaves of potted cucumber seedlings of the cultivar “Chinese Snake”were, at the cotyledon stage, sprayed to runoff point with an aqueouspreparation of active compound which had been prepared from a stocksolution comprising 10% of active compound, 85% of cyclohexanone and 5%of emulsifier 20 hours after the spray coating had dried on, the plantswere inoculated with an aqueous spore suspension of mildew of cucumber(Sphaerotheca fuliginea). The plants were then cultivated in agreenhouse at 20-24° C. and 60-80% relative atmospheric humidity for 7days. The extent of the mildew development was then determined visuallyin % infection of the cotyledon area.

In this test, the plants which had been treated with 250 ppm of theactive compounds Nos. 86, 88, 100, 121, 130, 141, 160, 163, 168, 171,185, 186, 189, 206, 220, 249, 253 to 261, 265, 266, 271, 273, 275, 276,287 and 299 of Table I showed an infection of not more than 10%, whereasthe untreated plants were 85% infected.

1-11. (canceled)
 12. A 5-phenylpyrimidine of the formula I

where the substituents and the index are as defined below: R¹ isC₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halo-cycloalkyl,C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl or C₂-C₆-haloalkynyl, R²is hydrogen or a group as defined for R¹, or R¹ and R² together with thenitrogen atom to which they are attached may also form a saturated orunsaturated five- or six-membered ring which may be interrupted by anether- (—O—), thio- (—S—), sulfoxyl- (—S[═O]—) or sulfenyl- (—SO₂—)group and/or may be substituted by one to four groups R^(a) and/or Rb;R^(a), R^(b) independently of one another are hydrogen, C₁-C₆-alkyl,C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkoxy, C₃-C₁o-cycloalkyl, phenyl or a five- to ten-memberedsaturated, partially unsaturated or aromatic heterocycle containing oneto four heteroatoms from the group consisting of O, N and S, where thecyclic radicals may be partially or fully substituted by the followinggroups R^(x); or R^(a) and R^(b) together, via an alkylene or alkenylenechain with the bridging atom, may also form a saturated or unsaturatedrated 5- or 6-membered ring; R^(x) independently of one another arecyano, nitro, amino, aminocarbonyl, aminothiocarbonyl, halogen,hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylcarbonyl,C₁-C₆-alkylsulfonyl, C_(l)-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkyloxycarbonyl, C₁-C₆-alkylthio,C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkylaminocarbonyl,di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkylaminothiocarbonyl,di-C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,phenyl, phenoxy, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or6-membered hetaryl, 5- or 6-membered hetaryloxy, C(═NOR^(α))—OR^(β)orOC(R^(α))₂—C(R^(β))═NOR^(β), where the cyclic groups for their part areunsubstituted or substituted by one to three radicals R^(y); R^(y) iscyano, nitro, halogen, hydroxyl, amino, aminocarbonyl,aminothiocarbonyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylsulfonyl,C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino,di-C₁-C₆-alkylamino, C₁-C₆-alkylaminocarbonyl,di-C₁-C₆-alkylaminocarbonyl, C_(l)-C₆-alkylaminothiocarbonyl,di-C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl, phenyl, phenoxy, phenylthio,benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-memberedhetaryl, 5- or 6-membered hetaryloxy or C(═NOR^(α)) —OR^(β); R^(α),R^(β)are hydrogen or C₁-C₆-alkyl; R³ is hydrogen, halogen, cyano,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy orC₃-C₈-alkenyloxy; R⁴ is hydrogen, halogen, cyano, hydroxyl, mercapto,azido, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C_(l)-C₆-haloalkyl, C₁-C₆-alkoxy,C₃-C₈-alkenyloxy, C₁-C₆-haloalkoxy, C₃-C₈-alkenylthio,C₃-C₈-alkynylthio, —ON═CR^(a)R^(b), —CRC═NOR^(a), —NR^(c)N═CR^(a)R^(b),—NR^(c)NR^(a)R^(b), —NHOR^(a), —NR^(c)C(═NR^(c))NR^(a)R^(b),—NR^(c)C(═O)NR^(a)R^(b), —NR^(a)C(═O)R^(c), —NR—^(a)C(═NOR^(c))R^(c)′,—OC(═O)R^(c), —C(═NOR^(c))NR^(a)R^(b), —CRC(═NNR^(a)R^(b)),—C(═O)NR^(a)R^(b) or —C(═O)R^(c); R^(c) is one of the monovalent groupsmentioned under R^(a) and R^(b); X is halogen, C₁-C₆-alkyl, C₁-C₆-alkoxyor C₁-C₆-haloalkyl; and m is an integer from 1 to
 5. 13. A5-phenylpyrimidine of the formula I

where the substituents and the index are as defined below: R¹ isC₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halo-cycloalkyl,C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl or C₂-C₆-haloalkynyl, R²is hydrogen or a group as defined for R¹, or R¹ and R² together with thenitrogen atom to which they are attached may also form a saturated orunsaturated five- or six-membered ring which may be interrupted by anoxygen atom and which may carry a C₁-C₆-alkyl substituent or in whichtwo adjacent carbon ring members may be bridged by a C₁-C₄-alkylenegroup; R³ is hydrogen, halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or C₃-C₈-alkenyloxy; R⁴ is hydrogen,halogen, cyano, hydroxyl, mercapto, azido, C₂-C₈-alkenyl, C₂-C₈-alkynyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₃-C₈-alkenyloxy, C₁-C₆-haloalkoxy,C₃-C₈-alkenylthio, C₃-C₈-alkynylthio, —ON═CR^(a)R^(b), —CR^(a)═NOR^(b),—NR^(a)N═CR^(a)R^(b), —NR^(a)NR^(a)R^(b) or —NHOR^(a); R^(a), R^(b)independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₈-alkenyl,C₂-C₈-alkynyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₃-C₁o-cycloalkyl, phenyl or a five- to ten-membered saturated,partially unsaturated or aromatic heterocycle containing one to fourheteroatoms from the group consisting of O, N and S, where the cyclicradicals may be partially or fully substituted by the following groupsR^(x); Rx independently of one another are cyano, nitro, amino,aminocarbonyl, aminothiocarbonyl, halogen, hydroxyl, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkylcarbonyl, C_(l)-C₆-alkylsulfonyl,C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkyloxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino,di-C₁-C₆-alkylamino, C_(l)-C₆-alkylaminocarbonyl,di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkylaminothiocarbonyl,di-C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,phenyl, phenoxy, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or6-membered hetaryl, 5- or 6-membered hetaryloxy, C(═NOR^(α))—OR^(β) orOC(R^(α))₂—C(R^(β))═NOR^(β), where the cyclic groups for their part areunsubstituted or substituted by one to three radicals R^(y); R^(y) iscyano, nitro, halogen, hydroxyl, amino, aminocarbonyl,aminothiocarbonyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylsulfonyl,C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino,di-C₁-C₆-alkylamino, C₁-C₆-alkylaminocarbonyl,di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkylaminothiocarbonyl,di-C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,C₃-C₆-cycloalkyl, C₃-C₆-cycloalkenyl, phenyl, phenoxy, phenylthio,benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-memberedhetaryl, 5- or 6-membered hetaryloxy or C(═NOR^(α))—OR^(β); R^(α), R^(β)are hydrogen or C₁-C₆-alkyl; X is halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy orC₁-C6-haloalkyl; and m is an integer from 1 to
 5. 14. A compound of theformula I as claimed in claim 12, in which R⁴ is hydrogen, cyano, azido,C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₁-C₆-haloalkyl, —CR^(c)═NOR^(c),—ON═CR^(a)R^(b), —NR^(c)N═CR^(a)R^(b) or —C(═NOR^(c))NR—^(a)R^(b).
 15. Aprocess for preparing a compound of the formula I as claimed in claim 12where R⁴ is cyano or one of the groups bound via a heteroatom, whichcomprises reacting a sulfone of the formula II,

in which R is C₁-C₄-alkyl, with a compound of the formula IIIR⁴—H  III in which R⁴ is as defined above under basic conditions.
 16. Aprocess for preparing a compound of the formula I as claimed in claim 12where R³ is cyano, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or C₃-C₈-alkenyloxy,which comprises reacting a pyrimidine of the formula I in which R³ ishalogen with a compound of the formula IXR³—H  IX in which R³ is as defined above under basic conditions.
 17. Aprocess for preparing a compound of the formula I as claimed in claim 12where R³ is C₁-C₆-alkyl, which comprises reacting a pyrimidine of theformula I in which R³ is halogen with an organometallic compound of theformula XR³—M  X in which M is a group Mg-Hal, Zn—R³ or B(OR)₂, where Hal is ahalogen atom and R is hydrogen or C₁-C₄-alkyl and R3 is C₁-C₆-alkyl.